CN115477946A - Green fluorescent material for non-contact temperature sensor and preparation method thereof - Google Patents
Green fluorescent material for non-contact temperature sensor and preparation method thereof Download PDFInfo
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- 239000010431 corundum Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
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- 238000005245 sintering Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 7
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- KQUQKVGNBPTEFO-UHFFFAOYSA-L n,n-dimethylcarbamodithioate;manganese(2+) Chemical compound [Mn+2].CN(C)C([S-])=S.CN(C)C([S-])=S KQUQKVGNBPTEFO-UHFFFAOYSA-L 0.000 description 1
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Abstract
The application discloses a green fluorescent material for a non-contact temperature sensor and a preparation method thereof, wherein the chemical formula of the green fluorescent material is ALa (1‑x) Er x LiTeO 6 Wherein A is any one of Ba, sr, ca or Mg. The fluorescent powder material has high color purity which is respectively as high as 95%,96%,98% and 97%. In addition, due to two thermally coupled excited state energy levels of rare earth Er ions(s) ((s)) 2 H 11/2 And 4 S 3/2 ) The series of fluorescent powder materials doped with Er ions can be used for the research of a non-contact temperature sensor along with the special relation of temperature change.
Description
Technical Field
The application relates to the technical field of rare earth luminescent materials and non-contact temperature sensing, in particular to a green fluorescent material for a non-contact temperature sensor and a preparation method thereof.
Background
Temperature plays an important role as a thermodynamic physical quantity in biomedicine, industrial production, and human daily life. Conventional contact thermometers, such as liquid filled glass thermometers, thermocouples, thermal resistors, and the like, have been the primary temperature measuring devices for the last several decades. Conventional contact thermometers based on the principle of thermal equilibrium between the sensor and the object typically require convective heat transfer to effect the temperature measurement, which can result in a change in the local temperature of the measured object during the measurement.
Moreover, these thermometers are not easily miniaturized and cannot be used for temperature measurement of batteries, minute electronic components, fast moving objects, and the like. In addition, the existing thermometer cannot meet the temperature control and measurement requirements under extreme conditions such as corrosive environment and electromagnetic interference environment. Therefore, it is of great practical significance to develop a non-contact temperature sensor with high precision and high sensitivity.
Non-contact optical temperature sensors are an effective way to make temperature measurements under extreme conditions, micro-scale environments and other special circumstances. In the non-contact optical thermometer, various optical temperature sensing methods based on the characteristics of fluorescence intensity, emission bandwidth, fluorescence lifetime, and Fluorescence Intensity Ratio (FIR) have been used for measuring temperature of rare earth ion-doped phosphor. In addition, compared with the conventional thermal sensor, the sensor based on the FIR principle has higher durability, higher spatial resolution and large-scale real-time monitoring imaging function.
The rare earth fluorescent material can be used for white light LED illumination, and can be applied to the field of temperature sensing when a specific functional relation exists between the fluorescence characteristic and the temperature.
Due to two thermally coupled excited state energy levels of rare earth Er ions: ( 2 H 11/2 And 4 S 3/2 ) To the ground state ( 4 I 15/2 ) Caused by transition emissionTwo very strong green emission bands and a suitable energy difference between the two excited states (. DELTA.E.apprxeq.700 cm) -1 ) Therefore, er ions are potentially useful for non-contact temperature sensors.
At present, many Er ion doped green luminescent materials which can be applied to the temperature sensing field have been synthesized and reported at home and abroad. For example, in 2018, j.manam et al synthesized BaTiO 3 Er upconversion green emitting material with absolute sensitivity of 0.0032K -1 . In 2020, zhang et al synthesized GaTaO 4 Er up-conversion green luminescent material, the absolute sensitivity and the relative sensitivity of which can reach 0.0041K respectively -1 And 0.0112K -1 . In 2021, hua et al reported a La 2 MgTiO 6 Er green luminescent material, its absolute sensitivity and relative sensitivity can reach 0.00963K -1 And 0.01107K -1 The method can be applied to optical temperature sensors.
The prior art CN201911057720.0 discloses a near-ultraviolet excited green phosphor for a non-contact temperature detector. The chemical expression of the green fluorescent powder is SrLa 1-x Er x AlO 4 Wherein x is more than or equal to 0.01 and less than or equal to 0.07. The fluorescent powder has rich excitation spectrum, has stronger excitation peaks at 356nm, 365nm, 377nm and 488nm, has the highest luminous intensity of the excitation peak at 377nm, obtains emission peaks at 528nm and 548nm, and is suitable for being used as near-ultraviolet excited green fluorescent powder. Additionally, due to two thermally coupled excited state energy levels of Er ions: ( 2 H 11/2 And 4 S 3/2 ) Can be used as a non-contact temperature detector, but the claimed sensitivity in this technique can reach 1.42% -1 Absolute or relative sensitivity is not indicated and color purity data of the resulting phosphor is not disclosed.
Disclosure of Invention
The application provides a green fluorescent material for a non-contact temperature sensor and a preparation method thereof, the color purity of the obtained green fluorescent material is respectively as high as 95%,96%,98% and 97%, and two thermal coupling excited state energy levels of Er ions in the material are (energy level of) and (energy level of) are (energy level of) a thermal coupling excited state of the Er ions 2 H 11/2 And 4 S 3/2 ) To the ground state ( 4 I 15/2 ) The transition emission has a specific functional relation with the temperature, and the absolute sensitivity of the series of materials can reach: 0.0103K -1 ，0.0120K -1 ，0.00706K -1 ，0.00603K -1 The relative sensitivity can reach: 0.0107K -1 ，0.0120K -1 ，0.0112K -1 ，0.0115K -1 The series of materials can be used in the field of non-contact temperature sensing.
The application provides a green fluorescent material for a non-contact temperature sensor, and the chemical formula of the green fluorescent material is ALa (1-x) Er x LiTeO 6 Wherein A is any one of Ba, sr, ca or Mg; wherein x is more than or equal to 0.01 and less than or equal to 0.15.
Preferably, x =0.06.
Specifically, the chemical formula of the green fluorescent material is BaLa 0.94 LiTeO 6 :6％Er 3+ (BLLT:6％Er 3+ )，SrLa 0.94 LiTeO 6 :6％Er 3+ (SLLT:6％Er 3+ )，CaLa 0.94 LiTeO 6 :6％Er 3+ (CLLT:6％Er 3+ )，MgLa 0.94 LiTeO 6 :6％Er 3+ (MLLT:6％Er 3+ ). The series of green fluorescent materials are all prepared by a high-temperature solid-phase method.
The green fluorescent material with the structure can obtain strong green light emission at 526nm and 547nm under the excitation of 379nm near ultraviolet light, and the fluorescent powder can be used as a green light-emitting fluorescent powder raw material of a white light-emitting LED. Two thermally coupled excited state energy levels of Er ions in the phosphor powder (C:) 2 H 11/2 And 4 S 3/2 ) To the ground state ( 4 I 15/2 ) The transition emission capability and the temperature have a specific functional relationship, and the method can be used in a non-contact temperature sensor.
Meanwhile, the obtained fluorescent powder has high color purity, and the absolute sensitivity can reach: 0.0103K -1 ，0.0120K -1 ，0.00706K -1 ，0.00603K -1 The relative sensitivity can reach: 0.0107K -1 ，0.0120K -1 ，0.0112K -1 ，0.0115K -1 The material is used as the raw material of the non-contact temperature measuring sensor, the sensitivity is high, and the detection accuracy is high.
Another aspect of the present application further provides a method for preparing the above fluorescent material, including the following steps: all the raw materials are weighed according to molar ratio and then uniformly mixed to prepare the catalyst by adopting a high-temperature solid-phase synthesis method.
Preferably, the feedstock substances include: la source substance, li source substance, te source substance, er source substance and A source substance; the A source material is one of Ba source material, sr source material, ca source material and Mg source material.
Preferably, the La source substance is La 2 O 3 (ii) a The Li source substance is Li 2 CO 3 (ii) a The Te source substance is TeO 2 (ii) a The Er source substance is Er 2 O 3 。
Preferably, the Ba source is BaCO 3 (ii) a The Sr source substance is SrCO 3 (ii) a The Ca source substance is CaCO 3 (ii) a The Mg source is MgCO 3 。
Preferably, the feedstock substance is BaCO 3 、La 2 O 3 、Li 2 CO 3 、TeO 2 、Er 2 O 3 ，BaCO 3 ：La 2 O 3 ：Li 2 CO 3 ：TeO 2 ：Er 2 O 3 In a molar ratio of 1:0.47:0.5:1:0.03.
preferably, the starting material is SrCO 3 、La 2 O 3 、Li 2 CO 3 、TeO 2 、Er 2 O 3 ，SrCO 3 ：La 2 O 3 ：Li 2 CO 3 ：TeO 2 ：Er 2 O 3 In a molar ratio of 1:0.47:0.5:1:0.03.
preferably, the feedstock substance is CaCO 3 、La 2 O 3 、Li 2 CO 3 、TeO 2 、Er 2 O 3 ，CaCO 3 ：La 2 O 3 ：Li 2 CO 3 ：TeO 2 ：Er 2 O 3 In a molar ratio of 1:0.47:0.5:1:0.03。
preferably, the raw material substance is MgO, la 2 O 3 、Li 2 CO 3 、TeO 2 、Er 2 O 3 ，MgO：La 2 O 3 ：Li 2 CO 3 ：TeO 2 ：Er 2 O 3 In a molar ratio of 1:0.47:0.5:1:0.03.
the raw materials are mixed according to the molar ratio, and a green fluorescent powder material with better color purity and higher sensitivity can be prepared by adopting a high-temperature solid-phase synthesis method.
The molar ratios obtained by the calculation are accurately weighed according to the stoichiometric ratios: baCO 3 ，SrCO 3 ，CaCO 3 ，MgCO 3 ，La 2 O 3 ，Li 2 CO 3 ，TeO 2 And Er 2 O 3 。
Preferably, the high temperature solid phase synthesis method comprises the steps of:
(1) Grinding: uniformly mixing the raw material substances, and fully grinding the raw material substances in an agate mortar for 30min to obtain a reactant;
(2) Pre-sintering: putting the reactants into a corundum crucible, placing the corundum crucible into a muffle furnace, heating for 300min, raising the temperature in the muffle furnace to 600 ℃, and preserving the temperature for 360min;
(3) And (3) re-sintering: and continuously heating for 500min, raising the temperature to 1000-1050 ℃, preserving the heat for 300-600 min, and then cooling to room temperature along with the furnace to obtain the fluorescent material.
Preferably, when the source substance A is a source substance Ba, the temperature is raised to 1000 ℃ in the step (3).
Preferably, when the a source substance is any one of a Sr source substance, a Ca source substance, or a Mg source substance, the temperature is raised to 1050 ℃ in step (3).
In the pre-sintering and re-sintering stages, in order to ensure that all raw materials can fully react under the high-temperature reaction condition, the grinding times and time in the step (1) can be increased, so that the powder reaction is more uniform, and a target powder sample is finally obtained.
The beneficial effects that this application can produce include:
1) The application provides a be used for contactless temperature sensorThe green fluorescent material has the color purity respectively as high as 95%,96%,98% and 97%, and has higher color purity, thereby being beneficial to improving the measurement sensitivity of the fluorescent powder when being used as a raw material for preparing a non-contact temperature sensor. And two thermally coupled excited state energy levels of Er ions in the obtained phosphor material (b: (b)) 2 H 11/2 And 4 S 3/2) to the ground state ( 4 I 15/2 ) The functional relation between the transition emission and the temperature meets the requirements of non-contact temperature sensing raw materials, and the absolute sensitivity of the fluorescent powder obtained in each embodiment can reach: 0.0103K -1 ，0.0120K -1 ，0.00706K -1 ，0.00603K -1 The relative sensitivity can reach: 0.0107K -1 ，0.0120K -1 ，0.0112K -1 ，0.0115K -1 The series of materials can be used in the field of non-contact temperature sensing, and can effectively improve the temperature measurement sensitivity and accuracy of the obtained sensor when being used as a raw material for preparing the sensor.
2) According to the green fluorescent material for the non-contact temperature sensor, the fluorescent powder material is excited by 379nm near ultraviolet light to obtain strong green light emission at 526nm and 547nm positions, and can be used as a green fluorescent powder light emitting part of a white light emitting LED.
3) The green fluorescent material preparation method for the non-contact temperature sensor provided by the application adopts a high-temperature solid phase method, the fluorescent material can be obtained only by grinding, presintering and sintering, the synthesis method has the advantages of low raw material price, low production cost, simplicity and convenience in operation, and a device required by reaction has a simple structure, and is suitable for mass industrial production.
Drawings
FIG. 1 shows the% of BLLT:6 Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ An XRD pattern of (a);
FIG. 2 shows the% of BLLT:6 Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ Under the temperature of 298-573K, the wavelength range is 500-600 nmInjection pattern, wherein (a) is BLLT:6% Er 3+ The variable temperature emission profile of (a), (b) SLLT:6% 3+ The variable temperature emission spectrum of (c) is CLLT:6% Er 3+ The variable temperature emission spectrum of (d) is MLLT:6% Er 3+ The variable temperature emission spectrum of (2);
FIG. 3 shows the% of BLLT:6 Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ The fluorescence intensity ratio map of (a);
FIG. 4 shows BLLT:6% Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ Absolute sensitivity spectrum of (a);
FIG. 5 shows the 6% of BLLT obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT 6% Er 3+ Relative sensitivity profiles of (a).
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Technical means which are not described in detail in the present application and are not intended to solve the technical problems of the present application are provided according to common general knowledge in the art, and various common general knowledge arrangement modes can be implemented.
Examples
The materials used in the following examples were all commercially available, unless otherwise specified.
The phosphor is BLLT:6% Er 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT 6% Er 3+ All samples were synthesized using high temperature solid phase.
Example 1 preparation of BLLT 6% Er 3+ Fluorescent powder:
(1) Weighing: accurately weighing 0.7067g BaCO according to the stoichiometric ratio 3 (99.0％)、0.5484gLa 2 O 3 (99.99％)、0.1323gLi 2 CO 3 (99.99％)、0.5715gTeO 2 (99.99％)、0.0411gEr 2 O 3 (99.99％)；
(2) Grinding: mixing all the raw materials, fully grinding the raw materials in an agate mortar for 30min, and putting reactants into a corundum crucible after grinding;
(3) And (3) a pre-sintering stage: putting the corundum crucible containing the reactants into a muffle furnace, heating to 600 ℃ after 300min, and preserving heat for 360min;
(4) And (3) a re-sintering stage: and (3) putting the corundum crucible containing the reactants into a muffle furnace, heating for 500min to 1000 ℃, preserving heat for 600min, and then cooling to room temperature along with the furnace to finally obtain a target powder sample.
Example 2 preparation of SLLT:6% Er 3+ Fluorescent powder:
(1) Weighing: accurately weighing 0.5803gSrCO according to the stoichiometric ratio 3 (99％)、0.6020gLa 2 O 3 (99.99％)、0.1452gLi 2 CO 3 (99.99％)、0.6274gTeO 2 (99.99％)、0.0451gEr 2 O 3 (99.99％)；
(2) Grinding: mixing all the raw materials, fully grinding the mixture in an agate mortar for 30min, and after grinding, putting reactants into a corundum crucible;
(3) And (3) a pre-sintering stage: putting the corundum crucible containing the reactants into a muffle furnace, heating for 300min, raising the temperature in the muffle furnace to 600 ℃, and keeping the temperature for 360min;
(4) And (3) a re-sintering stage: and (3) putting the corundum crucible containing the reactants into a muffle furnace, heating for 500min to 1050 ℃, preserving heat for 300min, and then cooling to room temperature along with the furnace to finally obtain a target powder sample.
Example 3 preparation of CLLT 6% Er 3+ Fluorescent powder:
(1) Weighing: accurately weighing 0.4340g of CaCO according to the stoichiometric ratio 3 (99.0％)、0.6640gLa 2 O 3 (99.99％)、0.1602gLi 2 CO 3 (99.99％)、0.6920gTeO 2 (99.99％)、0.0498gEr 2 O 3 (99.99％)；
(2) Grinding: mixing all the raw materials, fully grinding the mixture in an agate mortar for 30min, and after grinding, putting reactants into a corundum crucible;
(3) And (3) a pre-sintering stage: putting the corundum crucible containing the reactants into a muffle furnace, heating for 300min, raising the temperature in the muffle furnace to 600 ℃, and keeping the temperature for 360min;
(4) And (3) a re-sintering stage: and (3) putting the corundum crucible containing the reactants into a muffle furnace, heating for 500min to 1050 ℃, preserving heat for 300min, and then cooling to room temperature along with the furnace to finally obtain a target powder sample.
Example 4 preparation of MLLT:6% Er 3+ Fluorescent powder:
(1) Weighing: accurately weighing 0.3785g MgCO according to the stoichiometric ratio 3 (98％)、0.6875gLa 2 O 3 (99.99％)、0.1659gLi 2 CO 3 (99.99％)、0.7166gTeO 2 (99.99％)、0.0515gEr 2 O 3 (99.99％)；
(2) Grinding: mixing all the raw materials, fully grinding the mixture in an agate mortar for 30min, and after grinding, putting reactants into a corundum crucible;
(3) And (3) a pre-sintering stage: putting the corundum crucible containing the reactants into a muffle furnace, heating for 300min, raising the temperature in the muffle furnace to 600 ℃, and keeping the temperature for 360min;
(4) And (3) a re-sintering stage: and (3) putting the corundum crucible containing the reactants into a muffle furnace, heating for 500min to 1050 ℃, preserving heat for 300min, and then cooling to room temperature along with the furnace to finally obtain a target powder sample.
Example 5 preparation of Bala 0.99 Er 0.01 LiTeO 6
The difference from example 1 is that: accurately weighing 0.7085g BaCO according to the stoichiometric ratio in the step (1) 3 (99.0％)、0.5790gLa 2 O 3 (99.99％)、0.1326gLi 2 CO 3 (99.99％)、0.5730gTeO 2 (99.99％)、0.0069gEr 2 O 3 (99.99％)。
Example 6 preparation of Bala 0.85 Er 0.15 LiTeO 6
The difference from example 1 is that: accurately weighing 0.7035g BaCO according to the stoichiometric ratio in the step (1) 3 (99.0％)、0.4936gLa 2 O 3 (99.99％)、0.1317gLi 2 CO 3 (99.99％)、0.5689gTeO 2 (99.99％)、0.1023gEr 2 O 3 (99.99％)。
Example 7 preparation of SrLa 0.99 Er 0.01 LiTeO 6
The difference from example 2 is that: accurately weighing 0.5819g SrCO according to the stoichiometric ratio in the step (1) 3 (99％)、0.6357gLa 2 O 3 (99.99％)、0.1456gLi 2 CO 3 (99.99％)、0.6291gTeO 2 (99.99％)、0.0075gEr 2 O 3 (99.99％)。
Example 8 preparation of SrLa 0.85 Er 0.15 LiTeO 6
The difference from example 2 is that: accurately weighing 0.5774g SrCO according to the stoichiometric ratio in the step (1) 3 (99％)、0.5416gLa 2 O 3 (99.99％)、0.1445gLi 2 CO 3 (99.99％)、0.6243gTeO 2 (99.99％)、0.1122gEr 2 O 3 (99.99％)。
EXAMPLE 9 preparation of CaLa 0.99 Er 0.01 LiTeO 6
The difference from example 3 is that: in the step (1), 0.4353g of CaCO is accurately weighed in a stoichiometric ratio 3 (99.0％)、0.7015gLa 2 O 3 (99.99％)、0.1607gLi 2 CO 3 (99.99％)、0.6942gTeO 2 (99.99％)、0.0083gEr 2 O 3 (99.99％)。
EXAMPLE 10 preparation of CaLa 0.85 Er 0.15 LiTeO 6
The difference from example 3 is that: accurately weighing 0.4316g of CaCO according to the stoichiometric ratio in the step (1) 3 (99.0％)、0.5971gLa 2 O 3 (99.99％)、0.1593gLi 2 CO 3 (99.99％)、0.6882gTeO 2 (99.99％)、0.1237gEr 2 O 3 (99.99％)。
EXAMPLE 11 preparation of MgLa 0.99 Er 0.01 LiTeO 6
The difference from example 4 is that: in the step (1), 0.3797g of MgCO is accurately weighed according to the stoichiometric ratio 3 (98％)、0.7264gLa 2 O 3 (99.99％)、0.1664gLi 2 CO 3 (99.99％)、0.7188gTeO 2 (99.99％)、0.0086gEr 2 O 3 (99.99％)。
Example 12 preparation of MgLa 0.85 Er 0.15 LiTeO 6
The difference from example 4 is that: accurately weighing 0.3764gMgCO according to the stoichiometric ratio in the step (1) 3 (98％)、0.6181gLa 2 O 3 (99.99％)、0.1649gLi 2 CO 3 (99.99％)、0.7125gTeO 2 (99.99％)、0.1281gEr 2 O 3 (99.99％)。
The performance tests and the results of the phosphors obtained in examples 1 to 4 were as follows:
for the phosphor samples obtained in examples 1-4, respectively, there were prepared red phosphor NaGdTiO for white LED, such as Lemna minor, senajiu, chenlihong, sun Jia Shi, zhang jin Su, wang rank zhuo, chen Bao 4 :Eu 3+ Preparation and optical Properties [ J]138-143 of 2011 and 32 (02) and carrying out XRD detection, variable-temperature emission detection and variable-temperature emission spectrogram detection; wuzhong, wuhongmei, yaoqi, tanglidan, daxianchun, guognbo 4 :Er 3+ /Yb 3+ Upconversion luminescence and temperature characteristics of phosphors [ J ]]Absolute sensitivity detection, relative sensitivity detection is performed by the method disclosed in Luminology, 2017,38 (09): 1129-1135.
The results are shown in table 1 and fig. 1 to 5.
Analysis of the detection results of the phosphors obtained in examples 1 to 4:
the results obtained in examples 5 to 12 are similar to those in examples 1 to 4 and will not be described in detail here.
FIG. 1 shows the% of BLLT:6 Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ XRD pattern of (a). From the figure, it can be seen that BLLT:6% Er 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ Position of diffraction peak and BalAlTeO 6 (JCPDSCardNO.80-0077, the figure is the map of number PDF # 80-0077) is consistent with the standard card, which indicates that the samples obtained in examples 1-4 are pure phases.
BLLT:6% Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT 6% Er 3+ Color coordinates and color purity.
TABLE 1
From the color coordinates (CIE color coordinates) of (0.2426, 0.7176), (0.2450, 0.7193), (0.2608, 0.7153), (0.2691, 0.7097) in table 1, it can be seen that the phosphors obtained in each example are located in the green region of the CIE color coordinates, and the color purity is as high as 95%,96%,98%, and 97%, respectively.
FIG. 2 shows the% of BLLT:6 Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ A variable temperature emission spectrum with a wavelength range of 500-600 nm at a temperature of 298-573K. As the intensity of the emission peak of the rare earth Er ion at the position of 526nm is increased along with the temperature under the temperature of 298-573K, the intensity of the emission peak is continuously enhanced, and the rare earth Er ion is in a rare earth metal ion pairThe emission peak intensity results were reversed at the 547nm position. Such materials can be applied to the research of non-contact temperature sensing performance based on fluorescence intensity ratio, and the series of fluorescent powder can be suitable for the green light emitting part of a white light LED.
FIG. 3 shows the% of BLLT:6 Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ Fluorescence intensity ratio maps of 526nm and 547nm in the temperature range of 298-573K, and nonlinear fitting is carried out on the data. The energy difference (delta E) between the two excited states is calculated to be 658cm respectively -1 ，739cm -1 ，694cm -1 ，708cm -1 . Due to the proper energy difference (Delta E) between the two excited states, the luminescence property meets the requirement of two thermal coupling excited state energy levels (delta E) of Er ions 2 H 11/2 And 4 S 3/2) to the ground state ( 4 I 15/2 ) The transition of (a) emits energy as a function of temperature, and thus the series of materials can be used for the study of temperature sensors.
FIG. 4 shows the% of BLLT:6 Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ Absolute sensitivity profile of (a). BLLT:6% Er 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3 + Absolute sensitivity at different temperatures, with a maximum of 0.0103K -1 ，0.0120K -1 ，0.00706K -1 ，0.00603K -1 . The series of fluorescent powder has higher absolute sensitivity, and can effectively improve the detection accuracy and sensitivity of the obtained sensor when being used for a non-contact temperature sensor.
FIG. 5 shows BLLT:6% Er% obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT 6% Er 3+ Relative sensitivity profiles of (a). BLLT:6% Er 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3 + The maximum value of the relative sensitivity at different temperatures is 0.0107K -1 ，0.0120K -1 ，0.0112K -1 ，0.0115K -1 . The series of fluorescent powder has higher relative sensitivity, is used for a non-contact temperature sensor, and can effectively improve the detection accuracy and sensitivity of the obtained sensor.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.
Claims (10)
1. A green fluorescent material for a non-contact temperature sensor, characterized in that the green fluorescent material has a chemical formula of ALa (1-x) Er x LiTeO 6 Wherein A is any one of Ba, sr, ca or Mg; wherein x is more than or equal to 0.01 and less than or equal to 0.15.
2. The green fluorescent material according to claim 1, wherein x =0.06.
3. A method for preparing a green fluorescent material for a non-contact temperature sensor according to any one of claims 1 or 2, comprising the steps of: all the raw materials are weighed according to molar ratio and then uniformly mixed to prepare the catalyst by adopting a high-temperature solid-phase synthesis method.
4. The method of claim 3, wherein the feedstock material comprises: la source substance, li source substance, te source substance, er source substance and A source substance;
the A source material is one of Ba source material, sr source material, ca source material and Mg source material.
5. The method according to claim 4, wherein the La source is La 2 O 3 (ii) a The Li source substance is Li 2 CO 3 (ii) a The Te source substance is TeO 2 (ii) a Er SourceA mass of Er 2 O 3 。
6. The production method according to claim 3, wherein the Ba source substance is BaCO 3 (ii) a The Sr source is SrCO 3 (ii) a The Ca source substance is CaCO 3 (ii) a The Mg source is MgCO 3 。
7. The method according to claim 3, wherein the raw material is BaCO 3 、La 2 O 3 、Li 2 CO 3 、TeO 2 、Er 2 O 3 ，BaCO 3 ：La 2 O 3 ：Li 2 CO 3 ：TeO 2 ：Er 2 O 3 In a molar ratio of 1:0.47:0.5:1:0.03.
preferably, the starting material is SrCO 3 、La 2 O 3 、Li 2 CO 3 、TeO 2 、Er 2 O 3 ，SrCO 3 ：La 2 O 3 ：Li 2 CO 3 ：TeO 2 ：Er 2 O 3 In a molar ratio of 1:0.47:0.5:1:0.03.
preferably, the feedstock substance is CaCO 3 、La 2 O 3 、Li 2 CO 3 、TeO 2 、Er 2 O 3 ，CaCO 3 ：La 2 O 3 ：Li 2 CO 3 ：TeO 2 ：Er 2 O 3 In a molar ratio of 1:0.47:0.5:1:0.03.
preferably, the feedstock substance is MgCO 3 、La 2 O 3 、Li 2 CO 3 、TeO 2 、Er 2 O 3 ，MgCO 3 ：La 2 O 3 ：Li 2 CO 3 ：TeO 2 ：Er 2 O 3 In a molar ratio of 1:0.47:0.5:1:0.03.
8. the method of claim 4, wherein the high temperature solid phase synthesis method comprises the steps of:
(1) Grinding: uniformly mixing the raw material substances, and fully grinding the raw material substances in an agate mortar for 30min to obtain a reactant;
(2) Pre-sintering: putting the reactants into a corundum crucible, placing the corundum crucible into a muffle furnace, heating for 300min, raising the temperature in the muffle furnace to 600 ℃, and preserving the temperature for 360min;
(3) And (3) re-sintering: and continuously heating for 500min, raising the temperature to 1000-1050 ℃, preserving the heat for 300-600 min, and then cooling to room temperature along with the furnace to obtain the fluorescent material.
9. The production method according to claim 8, wherein the temperature is raised to 1000 ℃ in step (3) when the source substance A is a source substance Ba.
10. The production method according to claim 8, wherein the temperature is raised to 1050 ℃ in step (3) when the A source is any one of Sr source, ca source, or Mg source.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02298578A (en) * | 1989-02-03 | 1990-12-10 | Eastman Kodak Co | X-ray intensifying screen and phosphor composition |
| CN102250616A (en) * | 2011-05-06 | 2011-11-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Double-perovskite structured red fluorescent powder as well as preparation method and application thereof |
| CN102295927A (en) * | 2011-09-20 | 2011-12-28 | 杭州电子科技大学 | Fluorescent powder for white LED (Light Emitting Diode) and preparation method thereof |
| WO2012065575A1 (en) * | 2010-11-19 | 2012-05-24 | 江门市科恒实业股份有限公司 | Process for preparing red fluorescent powder of low europium content |
| CN103627392A (en) * | 2013-11-19 | 2014-03-12 | 苏州大学 | Antimonate-based red phosphor powder and preparation method and application thereof |
| CN110257068A (en) * | 2019-05-21 | 2019-09-20 | 云南大学 | A kind of yellow green phosphate fluorescent and the preparation method and application thereof |
| CN110846035A (en) * | 2019-11-28 | 2020-02-28 | 云南大学 | Erbium ion activated fluorescent powder and preparation method thereof |
| US20210301204A1 (en) * | 2018-07-19 | 2021-09-30 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Borate fluorescent powder and preparing method thereof |
| CN114656964A (en) * | 2022-04-15 | 2022-06-24 | 辽宁大学 | Self-calibration fluorescence temperature measurement material and preparation method thereof |
-
2022
- 2022-09-30 CN CN202211209658.4A patent/CN115477946B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02298578A (en) * | 1989-02-03 | 1990-12-10 | Eastman Kodak Co | X-ray intensifying screen and phosphor composition |
| WO2012065575A1 (en) * | 2010-11-19 | 2012-05-24 | 江门市科恒实业股份有限公司 | Process for preparing red fluorescent powder of low europium content |
| CN102250616A (en) * | 2011-05-06 | 2011-11-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Double-perovskite structured red fluorescent powder as well as preparation method and application thereof |
| CN102295927A (en) * | 2011-09-20 | 2011-12-28 | 杭州电子科技大学 | Fluorescent powder for white LED (Light Emitting Diode) and preparation method thereof |
| CN103627392A (en) * | 2013-11-19 | 2014-03-12 | 苏州大学 | Antimonate-based red phosphor powder and preparation method and application thereof |
| US20210301204A1 (en) * | 2018-07-19 | 2021-09-30 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Borate fluorescent powder and preparing method thereof |
| CN110257068A (en) * | 2019-05-21 | 2019-09-20 | 云南大学 | A kind of yellow green phosphate fluorescent and the preparation method and application thereof |
| CN110846035A (en) * | 2019-11-28 | 2020-02-28 | 云南大学 | Erbium ion activated fluorescent powder and preparation method thereof |
| CN114656964A (en) * | 2022-04-15 | 2022-06-24 | 辽宁大学 | Self-calibration fluorescence temperature measurement material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 林河成;: "氧化镧的生产及应用发展", 上海有色金属 * |
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